10 research outputs found
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Enantioselective PCCP Brønsted acid-catalyzed aza-Piancatelli rearrangement.
An enantioselective aza-Piancatelli rearrangement has been developed using a chiral Brønsted acid based on pentacarboxycyclopentadiene (PCCP). This reaction provides rapid access to valuable chiral 4-amino-2-cyclopentenone building blocks from readily available starting material and is operationally simple
Cascade rearrangement of furylcarbinols with hydroxylamines: practical access to densely functionalized cyclopentane derivatives.
This article describes the aza-Piancatelli rearrangement with hydroxylamines to 4-aminocyclopentenones and subsequent transformations that highlight the versatility of the cyclopentene scaffold and the value of the hydroxylamine nucleophile in this transformation
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Cascade rearrangement of furylcarbinols with hydroxylamines: practical access to densely functionalized cyclopentane derivatives.
This article describes the aza-Piancatelli rearrangement with hydroxylamines to 4-aminocyclopentenones and subsequent transformations that highlight the versatility of the cyclopentene scaffold and the value of the hydroxylamine nucleophile in this transformation
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Importance of off-cycle species in the acid-catalyzed aza-Piancatelli rearrangement.
The observed rate of reaction in the dysprosium triflate catalyzed aza-Piancatelli rearrangement is controlled by a key off-cycle binding between aniline and catalyst. Deconvoluting the role of these ancillary species greatly broadens our understanding of factors affecting the productive catalytic pathway. We demonstrate that the rate of reaction is controlled by initial competitive binding between the furylcarbinol and nitrogen nucleophile using either a Brønsted or Lewis acid catalyst and that the resulting rearrangement proceeds without involving the Brønsted and Lewis acid catalyst. This shows conclusively that the rate-controlling step and selectivity of reaction are decoupled
ChemInform Abstract: Cascade Rearrangement of Furylcarbinols with Hydroxylamines: Practical Access to Densely Functionalized Cyclopentane Derivatives.
This article describes the aza-Piancatelli rearrangement with hydroxylamines to 4-aminocyclopentenones and subsequent transformations that highlight the versatility of the cyclopentene scaffold and the value of the hydroxylamine nucleophile in this transformation
Tandem Reaction Progress Analysis as a Means for Dissecting Catalytic Reactions: Application to the Aza-Piancatelli Rearrangement
Continuing developments
in the elucidation techniques of complex catalytic processes is of
foremost importance to modern synthetic chemistry, and the identification
of efficient synthetic techniques relies on precise, reliable, and
adaptable methods to dissect the mechanism of a given transformation.
Currently, methods of reaction development are grounded upon the systematic
modification of specific variablessuch as temperature, time,
concentration, etc.to account for and control the dynamic
series of coupled equilibria within a catalytic environment. On the
other hand, tandem reaction analytical methods that involve the concomitant
use of different instruments to probe a reaction can provide time-resolved
information regarding active chemical species and facilitate the interrogation
and optimization of the system. Herein, we report our study applying
tandem in situ ReactIR and HPLC-MS monitoring to the dysprosium(III)
triflate-catalyzed aza-Piancatelli rearrangement of 2-furylcarbinols,
a reaction that grants access to <i>trans</i>-4,5-disubstituted
cyclopentenonescommon motifs in important biologically relevant
and natural compounds. With a prototype automated sampling apparatus,
information was obtained about the intrinsic chemoselectivity of the
reaction, and previously unseen intermediates were observed, allowing
for a more detailed reaction mechanism to be substantiated. The advantages
of applying this type of tandem measurement to study these types of
systems are also discussed
Importance of Off-Cycle Species in the Acid-Catalyzed Aza-Piancatelli Rearrangement
The observed rate of reaction in
the dysprosium triflate catalyzed
aza-Piancatelli rearrangement is controlled by a key off-cycle binding
between aniline and catalyst. Deconvoluting the role of these ancillary
species greatly broadens our understanding of factors affecting the
productive catalytic pathway. We demonstrate that the rate of reaction
is controlled by initial competitive binding between the furylcarbinol
and nitrogen nucleophile using either a Brønsted or Lewis acid
catalyst and that the resulting rearrangement proceeds without involving
the Brønsted and Lewis acid catalyst. This shows conclusively
that the rate-controlling step and selectivity of reaction are decoupled
Importance of Off-Cycle Species in the Acid-Catalyzed Aza-Piancatelli Rearrangement
The observed rate of reaction in the dysprosium triflate catalyzed aza-Piancatelli rearrangement is controlled by a key off-cycle binding between aniline and catalyst. Deconvoluting the role of these ancillary species greatly broadens our understanding of factors affecting the productive catalytic pathway. We demonstrate that the rate of reaction is controlled by initial competitive binding between the furylcarbinol and nitrogen nucleophile using either a Brønsted or Lewis acid catalyst and that the resulting rearrangement proceeds without involving the Brønsted and Lewis acid catalyst. This shows conclusively that the rate-controlling step and selectivity of reaction are decoupled
Cascade rearrangement of furylcarbinols with hydroxylamines: practical access to densely functionalized cyclopentane derivatives
This article describes the aza-Piancatelli rearrangement with hydroxylamines to 4-aminocyclopentenones and subsequent transformations that highlight the versatility of the cyclopentene scaffold and the value of the hydroxylamine nucleophile in this transformation